Thermally stable, anthraquinone colorants containing copolymerizable vinyl groups

ABSTRACT

Disclosed are thermally-stable, anthraquinone colorant compounds (dyes) which contain one or more vinyl groups which render the compounds copolymerizable with reactive vinyl monomers to produce colored, polymeric compositions such as acrylate and methacrylate polymeric materials. The compounds possess good fastness (stability) to ultraviolet (UV) light, good solubility in vinyl monomers, good color strength and excellent thermal stability. Also disclosed are (1) coating composition comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the dye compounds described above, and (iii) a photoinitiator and (2) polymeric materials, i.e., polymers derived from one or more acrylic acid esters, one or more methacrylic acid esters, one or more other polymerizable vinyl compounds or mixtures of any two or more thereof, having copolymerized therein one or more of the anthraquinone colorant compounds.

CROSS REFERENCE TO RELATED APPLICATION

[0001] This application is a continuation-in-part of copendingapplication Ser. No. 09/633,548 filed Aug. 7, 2000.

FIELD OF THE INVENTION

[0002] This invention pertains to certain thermally-stable,anthraquinone colorant compounds (dyes) which contain one or more vinylgroups which render the compounds copolymerizable with reactive vinylmonomers to produce colored, polymeric compositions such as acrylate andmethacrylate polymeric materials. The compounds possess good fastness(stability) to ultraviolet (UV) light, good solubility in vinylmonomers, good color strength and excellent thermal stability. Thepresent invention includes acrylic polymeric materials, i.e., polymersderived from acrylic acid esters, methacrylic acid esters and/or othercopolymerizable vinyl compounds, having copolymerized therein one ormore of the dye compounds of the present invention.

BACKGROUND AND PRIOR ART

[0003] It is known (J. S. D. C., April 1977, pp 114-125) to producecolored polymeric materials by combining a reactive polymer suchterepolymers having epoxy groups or polyacryloyl chloride withanthraquinone dyes containing nucleophilic reactive groups such as aminoor hydroxy groups; to graft acryloylaminoanthraquinone dyes to thebackbone of vinyl or divinyl polymers; and to polymerize anthraquinonedyes containing certain olefinic groups to produce polymericdyes/pigments. U.S. Pat. No. 4,115,056 describes the preparation ofblue, substituted 1,4-diaminoanthraquinone dyes containing oneacryloyloxy group and and the use of the dyes in coloring variousfibers, especially polyamide fibers. U.S. Pat. No. 4,943,617 disclosesliquid crystalline copolymers containing certain blue, substituted1,5-diamino-4,8-dihydroxyanthraquinone dyes containing an olefinic groupcopolymerized therein to provide liquid crystal copolymers having highdichromism. U.S. Pat. No. 5,055,602 describes the preparation of certainsubstituted 1,4-diaminoanthraquinone dyes containing polymerizableacryloyl and methacryloyl groups and their use in coloring polyacrylatecontact lens materials by copolymerizing.

[0004] U.S. Pat. No. 5,362,812 discloses the conversion of a variety ofdye classes, including anthraquinones, into polymeric dyes by (a)polymerizing 2-alkenylazlactones and reacting the polymer with dyescontaining nucleophilic groups and by (b) reacting a nucleophilic dyewith an alkenylazlactone and then polymerizing the free radicallypolymerizable dyes thus produced. The polymeric dyes are reported to beuseful for photoresist systems and for colorproofing. U.S. Pat. No.5,367,039 discloses a process for preparing colored vinyl polymerssuitable for inks, paints, toners and the like by emulsionpolymerization of a vinyl monomer with reactive anthraquinone dyesprepared by functionalizing certain anthraquinone dyes with methacryloylgroups.

[0005] The preparation of a variety of dyes, including someanthraquinones, which contain photopolymerizable groups and their usefor color filters suitable for use in liquid crystal television sets,color copying machines, photosensitive resist resin compositions, andthe like are described in U.S. Pat. No. 5,578,419.

BRIEF SUMMARY OF THE INVENTION

[0006] One embodiment of the present invention concerns anthraquinonedye or colorant compounds represented by general Formulae I-XXI setforth below. The dyes having Formulae I-VII are blue-cyan colorants, thedyes having Formulae VIII-XVIII are red-magenta colorants, and the dyeshaving Formulae XIX-XXI are yellow colorants.

[0007] wherein:

[0008] R is selected from hydrogen or 1-3 groups selected fromC₁-C₆-alkyl, C₁-C₆-alkoxy and halogen;

[0009] R₁ is selected from C₁-C₆-alkyl, substituted C₁-C₆-alkyl,C₃-C₈-alkenyl, C₃-C₈-cycloalkyl, aryl and -L₁-Z-Q; R₂=selected fromhydrogen, C₁-C₆-alkyl, substituted C₁-C₆-alkyl, C₃-C₈-cycloalkyl andaryl;

[0010] R₃ and R₄ are independently selected from C₁-C₆-alkyl andbromine;

[0011] R₅ is selected from C₁-C₆-alkyl, substituted C₁-C₆ alkyl,C₃-C₈-cycloalkyl, aryl, heteroaryl, -L₁-Z-Q,

[0012] R₆ is selected from

[0013] R₇ is selected from hydrogen, substituted or unsubstitutedC₁-C₆-alkyl, C₁C₆-alkoxy, halogen, hydroxy, substituted or unsubstitutedC₁-C₆-alkylthio, sulfamoyl and substituted sulfamoyl;

[0014] R₈ is selected from hydrogen and C₁-C₆-alkyl;

[0015] R₉ is selected from the groups represented by R₁ and -L-Z-Q

[0016] R₁₀ is selected from hydrogen and halogen;

[0017] X is a covalent bond or a divalent linking group selected from—O—, —S—, —SO₂—, —CO₂—, —CON(Y)— and —SO₂N(Y)—, wherein Y is selectedfrom hydrogen, C₁-C₆-alkyl, substituted C₁-C₆-alkyl, C₃-C₈-cycloalkyl,C₃-C₈-alkenyl, aryl and -L-Z-Q;

[0018] X₁ is selected from —O—, —S—, —SO₂— and —SO₂N(Y)—;

[0019] X₂ is selected from —CO₂— and —SO₂N(Y₁), wherein Y₁ is a groupselected from hydrogen, C₁-C₆-alkyl, substituted C₁-C₆-alkyl,C₃-C₈-alkenyl, C₃-C₈-cycloalkyl, aryl heteroaryl and—CH₂-p-C₆H₄—C(R₈)═CH₂;

[0020] X₃ is selected from —CO₂—, —SO₂N(Y)—;

[0021] X₄ is selected from —CO₂—, —O— and —SO₂N(Y₁)—;

[0022] L is a divalent linking group selected from C₁-C₈-alkylene,C₁-C₆-alkylene-arylene, arylene, C₁-C₆-alkylene-arylene —C₁-C₆-alkylene,C₃-C₈-cycloalkylene, C₁-C₆-alkylene-C₃-C₈-cycloalkylene —C₁-C₆-alkylene,C₁-C₆-alkylene-Z₁-arylene-Z₁-C₁-C₆-alkylene andC₂-C₆-alkylene-[-Z₁-C₂-C₆-alkylene-]_(n)- wherein Z₁ is selected from—O—, —S— and —SO₂₋ and n is 1-3;

[0023] L₁ is a divalent linking group selected from C₂-C₆-alkylene,C₁-C₆-alkylene-C₃-C₈-cycloalkylene-C₁-C₆-alkylene,C₁-C₆-alkylene-arylene, C₃-C₈-cycloalkylene, andC₂-C₆-alkylene-[-Z₁-C₂-C₆-alkylene-]_(n)-;

[0024] L₂ is selected from C₂-C₆-alkylene, C₁-C₆-alkylene-arylene-C₁-C₆alkylene and C₁-C₆-alkylene-C₃-C₈-cycloalkylene-C₁-C₆-alkylene;

[0025] Z is a divalent group selected from —O—, —S—, —NH—,—N(C₁-C₆-alkyl)-, —N(C₃-C₈ alkenyl)-, —N(C₃-C₈ cycloalkyl)-, —N(aryl)-,—N(SO₂C₁-C₆-alkyl) and —N(SO₂ aryl)-, provided that when Q is aphotopolymerizable optionally substituted maleimide radical, Zrepresents a covalent bond; Q is an ethylenically-unsaturated,photosensitive polymerizable group; and

[0026] m and m₁ each is O or 1.

[0027] The ethylenically-unsaturated, photosensitive copolymerizablegroups represented by Q are selected from the following organicradicals:

[0028] wherein:

[0029] R₁₁ is selected from hydrogen and C₁-C₆-alkyl;

[0030] R₁₂ is selected from hydrogen; C₁-C₆-alkyl; phenyl and phenylsubstituted with one or more groups selected from C₁-C₆-aLkyl,C₁-C₆-alkoxy, —N(C₁-C₆-alkyl), nitro, cyano, C₁-C₆-alkoxycarbonyl,C₁-C₆-alkanoyloxy and halogen; 1- and 2-naphthyl which may besubstituted with C₁-C₆-alkyl or C₁-C₆-alkoxy; 2- and 3-thienyl which maybe substituted with C₁-C₆-alkyl or halogen; 2- or 3-furyl which may besubstituted with C₁-C₆-alkyl;

[0031] R₁₃ and R₁₄ are selected from hydrogen, C₁-C₆-alkyl, substitutedC₁-C₆-alkyl, aryl or may be combined to represent a —[—CH₂—]₃₋₅—radical;

[0032] R₁₅ is selected from hydrogen, C₁-C₆-alkyl, substitutedC₁-C₆-alkyl, C₃-C₈-alkenyl, C₃-C₈-cycloalkyl and aryl;

[0033] R₁₆ is selected from hydrogen, C₁-C₆-alkyl and aryl.

[0034] The term “C₁-C₆-alkyl” is used herein to denote a straight orbranched chain, saturated, aliphatic hydrocarbon radical containing oneto six carbon atoms. The term “substituted C₁-C₆-alkyl” is used todenote a C₁-C₆-alkyl group substituted with one or more groups,preferably one to three groups, selected from the group consisting ofhydroxy, halogen, cyano, aryl, aryloxy, arylthio, C₁-C₆ alkylthio,C₃-C₈-cycloalkyl, C₁-C₆-alkanoyloxy and —[—O—R₁₇—)—R₁₈, wherein R₁₇ isselected from the group consisting of C₁-C₆ alkylene,C₁-C₆-alkylene-arylene, cyclohexylene, arylene,C₁-C₆-alkylene-cyclohexylene andC₁-C₆-alkylene-cyclohexylene-C₁-C₆-alkylene;

[0035] R₁₈ is selected from the group consisting of hydrogen, hydroxy,carboxy, C₁-C₆-alkanoyloxy,

[0036] C₂-C₆-alkoxycarbonyl, aryl and C₃-C₈-cycloalkyl; and p is 1, 2,or 3.

[0037] A second embodiment of the present invention pertains to acoating composition comprising (i) one or more polymerizable vinylcompounds, (ii) one or more of the dye compounds described above, and(iii) a photoinitiator. A third embodiment of the present inventionpertains to a polymeric composition, typically a coating, comprising apolymer of one or more acrylic acid esters, one or more methacrylic acidesters and/or other polymerizable vinyl compounds, having copolymerizedtherein one or more of the dye compounds described above.

DETAILED DESCRIPTION

[0038] The terms “C₁-C₆-alkylene” and “C₁-C₈-alkylene” are used todenote straight or branched chain, divalent, aliphatic hydrocarbonradicals containing one to six and one to eight carbons, respectively,and these radicals substituted with one to three groups selected fromC₁-C₆-alkoxy, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkanoyloxy, hydroxy, aryl andhalogen. Similarly, the term “C₂-C₆-alkylene” is used to denote astraight or branched chain, divalent, hydrocarbon radical which may beunsubstituted or substituted as described in this paragraph for theC₁-C₆-alkylene and C₁-C₈-alkylene radicals.

[0039] The terms “C₁-C₆-alkoxy”, “C₁-C₆-alkoxycarbonyl”,“C₁-C₆-alkanoyloxy” and “C₁-C₆-alkanoylamino” are used to denoteradicals corresponding to the structures —OR₁₉, —CO₂ R₁₉, —OCOR₁₉ andNHCOR₁₉, respectively, wherein R₁₉ is C₁-C₆-alkyl or substitutedC₁-C₆-alkyl. The term “C₃-C₈-alkenyl” is used to denote an aliphatichydrocarbon radical containing at least one double bond. The term“C₃-C₈-cycloalkyl” is used to denote a saturated, carbocyclichydrocarbon radical having three to eight carbon which may beunsubstituted or substituted with one to three C₁-C₆-alkyl group(s). Theterm “C₃-C₈-cycloalkylene” is used to denote a carbocyclic, divalenthydrocarbon radical which contains three to eight carbon atoms,preferably five or six carbons.

[0040] The term “aryl” as used herein denotes phenyl and phenylsubstituted with one to three substituents selected from C₁-C₆-alkyl,substituted C₁-C₆-alkyl, C₁₋C₆₋alkoxy, halogen, carboxy, cyano,C₁-C₆-alkanoyloxy, C₁-C₆-alkylthio, C₁₋C₆₋alkylsulfonyl,trifluoromethyl, hydroxy, C₁-C₆-alkoxycarbonyl, C₁-C₆alkanoylamino and—O—R₂₀, S—R₂₀, —SO₂—R₂₀, —NHSO₂R₂₀ and —NHCO₂R₂₀, wherein R₂₀ is phenylor phenyl substituted with one to three groups selected fromC₁-C₆-alkyl, C₁-C₆-alkoxy and halogen. The term “arylene” as used hereindenotes includes 1,2-, 1,3- and 1,4-phenylene and such divalent radicalssubstituted with one to three groups selected from C₁-C₆-alkyl,C₁-C₆-alkoxy and halogen. The term “heteroaryl” as used herein denotes a5- or 6-membered aromatic ring containing one to three hetero atomselected from oxygen, sulfur and nitrogen. Examples of such heteroarylgroups are thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl,isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl,oxadiazolyl, tetrazolyl, pyridyl, pyrimidyl, benzoxazolyl,benothiazolyl, benzimidazolyl, indolyl and the like. The heteroarylradicals may be substituted with one to three groups selected fromC₁-C₆-alkyl, C₁-C₆-alkoxy, substituted C₁₋C₆-alkyl, halogen,C₁-C₆-alkylthio, aryl, arylthio, aryloxy, C₁-C₆-alkoxycarbonyl andC₁-C₆-alkanoylamino.

[0041] The term “halogen” is used to include fluorine, chlorine,bromine, and iodine. The terms “sulfamoyl and substituted sulfamoyl”denote radicals having the structure —SO₂N(R₂₁)R₂₂, wherein R₂₁ and R₂₂are independently selected from hydrogen, C₁-C₆-alkyl, substitutedC₁-C₆-alkyl, C₃-C₈-alkenyl, C₃-C₈-cycloalkyl, aryl and heteroaryl.

[0042] The preferred dye compounds of Formulae I, II, III, IV, V, VI,VIII, IX, X, XII, XIII, XIV, XVI, XVII, XIX, and XX are those where Z is—O—. These dyes are prepared by reacting the corresponding dihydroxy dye[Dye (OH)₂] with a reagent to introduce the reactive vinylfunctionality. For example, the dyes wherein Q corresponds to structureIa, VIa, XIa, respectively, are prepared by reacting the dihydroxy dyeswith the corresponding acid chlorides and/or anhydrides as follows:

[0043] The dyes wherein Z is —O— and Q corresponds to structures IIa,IIIa, and VIIIa are prepared by reacting the dihydroxy dyes with thecorresponding isocyanates:

[0044] The dyes were Z is —O— and where Q corresponds to structure IVaare prepared by reacting the dihydroxy dyes with 2-alkenylazlactones asgenerally described in Encyclopedia of Polymer Science and Eng., SecondEd., Vol. 11, John Wiley & Sons, pp. 558-571:

[0045] The dyes wherein Z is —O— and Q corresponds to structure Va aregenerally prepared by reacting the dihydroxy dyes with maleic anhydrideto give the mono maleate esters:

[0046] The remaining acid groups may be esterified by the usual typeesterification reactions such as heating in alcohols in the presence ofacid catalysts and reacting the alkali metal salts of the acids withalkylating agents such as alkyl halides, alkyl sulfates and alkylsulfonates, such as methyl 4-toluene sulfonate, to prepare the methylester. Fumaric acid and its derivatives also may be used to prepare thedyes where Q is radical Va. Itaconic anhydride (methylenesuccinicanhydride) may be used to react with the dihydroxy dyes to prepare thefunctionalized dyes wherein Z is —O— and Q corresponds to structure XIIa(R₁₅=H). These acidic compounds may be esterified as described above forpreparing the dyes where Q corresponds to structure Va.

[0047] Anthraquinone dyes containing aliphatic hydroxy groups useful forreacting as described above to produce dyes containing reactive Q groupsare disclosed in U.S. Pat. Nos. 4,267,306, 4,359,570, 4,403,092,4,804,719, 4,999,418, 5,032,670, 5,194,463, 5,372,864, 5,955,564 and5,962,557. Anthraquinone dyes containing 1(H)-1,2,4-triazol-3ylthiogroups which are useful in preparing dyes of Formulae III, IX, XIII andXX are disclosed in U.S. Pat. Nos. 3,689,501, 4,267,306, 5,962,557 andU.S. Pat. No. 6,197,223. Anthraquinone dyes containing carboxy groupsand which are useful in the practice of the invention are disclosed inU.S. Pat. Nos. 4,359,570, 4,403,092, 4,999,418, 5,372,864, 5,955,564,5,962,557 and U.S. Pat. No. 6,197,223. Hydroxy alkyl groups may beintroduced into these compounds by alkylation of the acids withhydroxyalkyl halides or alkylene carbonates to give the hydroxyalkylderivatives useful for reacting further as shown herein to introducereactive Q groups.

[0048] To prepare the dyes wherein Z is —S—, —NH—, —N(C₁-C₆ alkyl)-,—N(C₃-C₈ alkenyl)-, —N(C₃-C₈ cycloalkyl)-, —N(aryl)-, —N(SO₂ C₁-C₆alkyl)- and —N(SO₂ aryl)-, the corresponding anthraquinone dyescontaining two of the following nucleophilic ZH groups, respectively,are reacted with the reagents mentioned above for preparing the dyeswhere Z=—O—: —SH, —NH(C₁-C₆ alkyl), —NH(C₃-C₈ alkenyl), —NH(C₃-C₈cycloalkyl), —NH(aryl)-, NH(SO2 C₁-C₆ alkyl) and —NH(SO₂ aryl). All ofthe dyes mentioned above containing two ZH groups may be reacted withvinylsulfonyl halides to prepare dyes where Q=—SO₂C(R₁₁)=CH₂ (StructureIXa). When Q corresponds to Structure IXa, the preferred Z group is—NH—. Dyes wherein Q corresponds to structure Xa and XIIIa and Z is acovalent bond are prepared by reacting dyes containing two primary aminegroups with, for example, maleic anhydride and itaconic anhydride,respectively.

[0049] The functionalized dyes of Formulae VII, XI, XV, XVIII and XXIwherein X₂ and X₄ are —CO₂— are prepared by alkylating the intermediatedye containing two carboxy groups with an alkylating agent having thestructure ClCH₂-p-C₆H₄—C(R₈)═CH₂, with 4-vinylbenzyl chloride (R₈=H)being particularly preferred. The reaction is easily accomplished in thepresence of alkali metal carbonates and trialkyl amines as bases. Thefunctionalized dyes corresponding to Formulae III, IX, XIII and XXwherein m is 0 are prepared by reacting the intermediate dyes containingtwo 1(H)-1,2,4-triazol-3ylthio groups with an alkylating agent havingthe structure ClCH₂-p-C₆H₄—C(R₈)═CH₂, with 4-vinylbenzyl chloride (R₈=H)being preferred, in the presence of a base such as alkali metalcarbonates or trialkylamines.

[0050] A group of preferred anthraquinone compounds comprise compoundshaving structures XVI and XIX wherein X₃ is —CO₂—, L is propylene,1,4-cyclo-hexylenedimethylene or 2,2-dimethyltrimethylene, R ishydrogen, Z is —O—, and Q is an organic radical having the structure—COC(R₁₁)═CH₂ wherein R₁₁ is hydrogen, methyl or ethyl, or Q is anorganic radical having structure VIIIa wherein R₁₁, R₁₃ and R₁₄ each ismethyl.

[0051] The yellow, red-magenta, blue-cyan dyes of this invention areparticularly useful for making combination shades as subtractive colors.They have particular value for copolymerizing into acrylic polymericmaterials by free radical polymerization, having one or more advantagesover the prior art dyes such as thermal stability, solubility in theacrylate or methacrylate ester comonomer(s) to be used, fastness to UVlight, color strength, ease of manufacture and the like. The dyes ofthis invention are particularly useful for providing acrylic polymercolor coatings for glass optical fibers where good thermal stability ofdyes is required.

COLORANT EXAMPLES

[0052] The copolymerizable dye compounds provided by the presentinvention and the preparation thereof are further illustrated by thefollowing examples.

Example 1

[0053] A mixture of 1,5-bis-(2-carboxyphenylthio) anthraquinone (U.S.Pat. No. 4,359,570, Example 1) (5.13 g, 0.01 mol), potassium carbonate(2.84 g, 0.02 mol) and N,N-dimethylformamide (DMF, 100 mL) was stirredand heated to about 100° C. To the stirred mixture, was added4-vinylbenzyl chloride (Aldrich, 3.76 g, 0.022 m). Thin-layerchromatography (TLC) using a 50/50 mixture oftetrahydrofuran(THF)/cyclohexane after heating the reaction mixture atabout 105° C. for 30 min. showed only one spot with no starting materialor mono-reacted product being observed. The reaction mixture was heatedfor an additional 20 minutes and the yellow dye precipitated by theaddition of a mixture of methanol and water. The solid dye was collectedby filtration, washed with water and then with a little methanol. Theyield of air-dried product was 6.85 g (92% of the theoretical yield).Field desorption mass spectrometry (FDMS) supported the followingstructure:

[0054] An absorption maximum at 447 nm was observed in the UV-visibleabsorption spectrum in DMF.

Example 2

[0055] A mixture of 1,5-bis-(2-carboxyanilino) anthraquinone (U.S. Pat.No. 4,359,570, Example 2) (4.78 g, 0.01 mol), potassium carbonate (2.76g, 0.02 mol) and DMF (100 mL) was stirred and heated to about 90° C. and4-vinylbenzyl chloride (Aldrich, 3.76 g, 0.022 mol) was added andheating and stirring continued at about 100° C. for 60 min. TLC (50/50THF/cyclohexane) showed complete reaction. Methanol (120 mL) was addedgradually with stirring to precipitate the red product, which wascollected by filtration, washed with water and then dried in air(yield—6.18 g, 87% of the theoretical yield). FDMS supports thefollowing structure:

Example 3

[0056] A mixture of1,5-bis-(isobutylamino)-4,8-bis-(2-carboxyphenylthio) anthraquinone(U.S. Pat. No. 6,197,223, Example 2) (6.54 g, 0.01 mol), potassiumcarbonate (2.76 g, 0.02 m) and DMF (150 mL) was stirred and heated toabout 100° C. To the stirred reaction mixture was added 4-vinylbenzylchloride (3.76 g, 0.02 mol). The reaction mixture was heated at 95-100°C. for about 60 minutes The reaction mixture was cooled and the gummyproduct was drowned out by the addition of methanol/water. The liquidwas decanted off and the product triturated with methanol. The resultingdark blue solid was collected by filtration, washed with methanol anddried in air (yield—6.95 g, 78% of the theoretical yield). FDMSsupported the following structure:

[0057] Absorption maxima at 600 nm and 645 nm were observed in theUV-visible absorption spectra in DMF.

Example 4

[0058] A mixture of1,5-bis-(2-carboxyphenylthio)-4,8-bis-(4-tolylthio)-anthraquinone (U.S.Pat. No. 6,197,223) (7.56 g, 0.01 mol), potassium carbonate (K₂CO₃) andDMF (300 mL) was stirred and heated to about 100° C. and then4-vinylbenzyl chloride (3.84 g, 0.025 mol) was added. The reactionmixture was heated and stirred at about 100° C. for 60 minutes. TLC(50/50 THF/cyclohexanol) showed complete reaction. After cooling, thesticky product was obtained by drowning the reaction mixture withmethanol/water. The red product solidified upon standing in contact withmethanol and was collected by filtration and dried in air (yield—7.67 g,78% of the theoretical yield). FDMS supported the following structure:

[0059] An absorption maximum was observed at 520 nm in the UV-visibleabsorption in DMF.

Example 5

[0060] A mixture of 1,5-bis-[(1H)-1,2,4-triazol-3ylthio)] anthraquinone(U.S. Pat. No. 3,689,501) (4.06 g, 0.01 mol), potassium carbonate (2.76g, 0.02 mol) and DMF (100 mL) was stirred and heated to about 100° C.and 4-vinylbenzyl chloride (3.76 g, 0.022 mol) was added. TLC (50/50THF/cyclohexane) still showed some mono-substituted product afterheating the reaction mixture for 2 hrs. Additional quantities of4-vinylbenzyl chloride (4.14 g) and potassium chloride (1.38 g) wereadded and heating continued for another hour to complete the reaction. Agummy yellow solid was produced by drowning the cooled reaction mixturewith water. The product was washed by decantation with water and thendissolved in DMF. The DMF solution was drowned gradually into cold waterwith good stirring and the yellow solid was collected by filtration anddried in air (3.46 g, 54% of the theoretical yield). FDMS supported thefollowing structure:

[0061] An absorption maximum at 420 nm was observed in the UV-visibleabsorption spectrum in DMF.

Example 6

[0062] A mixture of 1,5-bis-(2,2-dimethyl-3-hydroxypropylamino)anthraquinone (U.S. Pat. No. 4,999,418, Example 1) (4.10 g, 0.01 mol),DMF (25 mL) and 3-isopropenyl-∝,∝-dimethylbenzyl isocyanate (Aldrich; 5mL, 0.025 mol) was heated and stirred at about 75° C. for 48 hrs. TLC(50/50-THF/cyclohexane) showed all of the starting material to bereacted and a mixture of the desired product plus the mono-reactionproduct. After addition of an additional quantity (1 mL) of3-isopropenyl-∝,∝-dimethylbenzyl isocyanate, the reaction mixture washeated and stirred at about 90° C. for 12 hrs. Triethylamine (0.5 mL)was added and the reaction mixture was stirred at about 100° C. foranother 24 hrs. The cooled reaction mixture was drowned into water (200mL) to produce a sticky solid which hardened upon standing. The waterwas decanted off and the solid redissolved in DMF (200 mL) by heating ona steambath. Water (50 mL) was added gradually to the hot DMF withstirring. After allowing to stand overnight a red solid had formed.Additional water (150 mL) was added and the product was collected byfiltration, washed with water and dried in air. Essentially aquantitative yield of the following product was obtained:

[0063] which was soluble in methanol, methylene chloride and somewhatsoluble in hexane.

Example 7a

[0064] A mixture of 1,5-bis-(2-carboxyphenylthio) anthraquinone (U.S.Pat. No. 4,359,570, Example 1) (30.6 g, 0.06 mol), ethylene carbonate(88.0 g, 1.0 mol), ethylene glycol (50 mL) and pulverized potassiumiodide (5.2 g) was heated and stirred at about 125° C. for about 2.0hours and then allowed to cool. The reaction mixture was drowned intocold water (150 mL) with stirring. The yellow solid was collected byfiltration, washed with warm water and dried in air (yield-35.2 g, 97.8%of the theoretical yield). FDMS supported the following structure:

Example 7b

[0065] A mixture of the product of Example 7a (6.0 g, 0.01 mol), DMF (25mL) and 3-isopropenyl-∝,∝-dimethylbenzyl isocyanate (6 mL, 0.03 mol) washeated and stirred, under nitrogen at about 95-100° C. for about 48hours. Triethylamine (0.5 mL) was added and heating continued for anadditional 48 hours. Water (60 mL) was added portionwise to the hotreaction mixture with stirring. After allowing to cool to roomtemperature, the yellow product was collected to filtration, washed withwater and dried in air. Essentially a quantitative yield of thefollowing product was obtained:

Example 8

[0066] A mixture of 1,5-bis-(2,2-dimethyl-3-hydroxypropylamino)anthraquinone (U.S. Pat. No. 4,999,418, Example 1) (1.0 g, 2.44 mmol)and toluene (50 mL) was prepared and then most of the toluene wasevaporated under reduced pressure to remove any water present. DMF (50mL), hydroquinone (50 mg), 4-(dimethyl-amino)pyridine (DMAP; 59.6 mg),triethylamine (1.0 mL) and methacrylic anhydride (1.33 g, 7.32 mmol)were added and the reaction mixture was stirred at room temperature forabout 20 hours. TLC (50/50 hexane/ethyl acetate) indicated completereaction. The reaction mixture was poured into water (300 mL) and thered product was collected by filtration, washed with water and dried invacuo (yield—1.30 g, 98% of the theoretical yield). FDMS supported thefollowing structure:

[0067] The functionalized red dye had an absorption maximum at 526 nm inDMF solution in the UV-visible absorption spectrum.

Example 9

[0068] The dye of Example 7a above (2.0 g, 3.33 mmol) and toluene (20mL) were mixed and stirred while most of the toluene was removed underreduced pressure. DMF (50 mL), DMAP (82 mg), triethylamine (1.4 mL),hydroquinone (50 mg) and methacrylic anhydride (1.53 g, 9.99 mmol) wereadded and the reaction mixture stirred at room temperature for 15 hours.The yellow functionalized dye which was precipitated by drowning intowater (200 mL) and allowing to stand for several days was collected byfiltration, washed with water and 1:1 methanol: water and dried invacuo. The yield was 2.23 g (91% of the theoretical yield). FDMSsupported the following structure:

[0069] An absorption maximum at 444 nm was observed in the UV-visibleabsorption spectrum in DMF.

Example 10a

[0070] A mixture of 1,5-bis-(carboxyanilino) anthraquinone (U.S. Pat.No. 4,359,570, Example 2) (59.75 g, 0.125 mol), ethylene carbonate (165g, 1.875 mol), ethylene glycol (550 mL) and pulverized potassium iodide(11.3 g) was heated at 120-125° C. for 6.5 hours and the mixture allowedto cool. Methanol (400 mL) was added to the stirred reaction mixture.The red solid was collected by filtration, washed with water and driedin air (yield—69.5 g, 98.2% of the theoretical yield). FDMS supportedthe following structure:

Example 10b

[0071] A portion (2.0 g, 3.53 mmol) of the dye of Example 10a above wasmixed with toluene (10 mL) and most of the toluene removed under vacuum.DMF (50 mL), DMAP (86 mg), triethylamine (1.5 mL), hydroquinone (20 mg)and methacrylic anhydride (1.63 g, 10.6 mmol) were added and theresulting solution was stirred for 15 hours at room temperature. Thereaction mixture was drowned into water (200) and allowed to stand atroom temperature for several days. The functionalized red dye wascollected by filtration, washed with water and dried in vacuo(yield—2.10 g. 85% of the theoretical yield). FDMS supported thefollowing structure:

[0072] An absorption maximum at 525 nm was observed in DMF solution inthe UV-visible absorption spectrum.

Example 11

[0073] A mixture of1,5-bis-(2,2-dimethyl-3-hydroxypropylamino)-4,8-bis-(tolylthio)anthraquinone(U.S. Pat. No. 5,955,564) (2.0 g, 3.06 mmol) and toluene (10 mL) wasstirred and most of the toluene removed under vacuum. DMF (50 mL),triethylamine (1.3 mL), DMAP (75 mg), hydroquinone (20 mg) andmethacrylic anhydride (1.41 g, 9.18 mmol) were added and the reactionmixture was stirred at room temperature for 15 hours. After drowninginto water (200 mL) and allowing the mixture to stand for several daysthe functionalized blue dye was collected by filtration, washed withwater and dried in vacuo. Essentially a quantitative yield was obtained.FDMS supported the following structure:

[0074] An absorption maximum at 650 nm was observed in DMF solution inthe UV-visible light absorption spectrum.

Example 12

[0075] A mixture of1,5-bis-[5-(N-ethyl-N-(2-hydroxyethyl)sulfamoyl)-2-methoxyanilino]anthraquinone(U.S. Pat. No. 5,372,864, Example 21) (2.0 g, 2.66 mmol) and toluene (10mL) was stirred and most of the toluene was removed under reducedpressure. DMF (50 mL), DMAP (65 mg), triethylamine (1.1 mL),hydroquinone (20 mg) and methacrylic anhydride (1.22 g, 7.98 mmol) wereadded and the reaction mixture was stirred overnight at room temperaturefor about 15 hours. The functionalized blue dye was precipitated bydrowning into water (200 mL) and allowing the mixture to stand forseveral days at room temperature and was collected by filtration washedwith water and dried in vacuo. Essentially a quantitative yield wasobtained. FDMS supported the following structure:

[0076] An absorption maximum at 527 nm in DMF solution was observed inthe UV-visible absorption spectrum.

Example 13

[0077] A portion (2.0 g, 3.53 mmol) of the dye from Example 10a abovewas mixed with toluene and stirred while most of the toluene was removedunder reduced pressure. DMF (50 mL), DMAP (86 mg), triethylamine (1.5mL), hydroquinone (20 mg) and crotonic anhydride (1.63 g, 10.6 mmol)were added and the reaction mixture was stirred for 24 hours. Thefunctionalized red dye was isolated by drowning into water (200 mL),allowing the mixture to stand for a little while and then collecting byfiltration. After washing with water the dye was dried in vacuo(yield—2.11 g, 85% of the theoretical yield). FDMS supported thefollowing structure:

[0078] An absorption maximum at 522 nm in DMF solution was observed inthe UV-visible light absorption spectrum.

Example 14

[0079] A mixture of1,5-bis-(2,2-dimethyl-3-hydroxypropylamino)-4,8-bis-(4-tolylthio)anthraquinone (U.S. Pat. No. 5,955,564) (2.0 g, 3.06 mmol) and toluene(10 mL) was stirred and most of the toluene removed under reducedpressure. DMF (50 mL), DMAP (75 mg), triethylamine (1.3 mL),hydroquinone (20 mg) and crotonic anhydride (1.41 g, 9.18 mmol) wereadded. The reaction mixture was stirred at room temperature for 24 hoursand then drowned into water (200 mL). After allowing the mixture tostand for awhile, the functionalized blue dye was collected byfiltration, washed with water and dried in vacuo. The yield wasessentially quantitative. FDMS supported the following structure:

[0080] An absorption maximum at 650 nm was observed in DMF in theUV-visible absorption spectrum.

Example 15

[0081] A mixture of 1,5-bis-[5-(N-ethyl-N-(2-hydroxyethyl)sulfamoyl-2-methoxyanilino]-anthraquinone (U.S. Pat. No. 5,372,864,Example 21) (2.0 g, 2.66 mmol) and toluene (10 mL) were stirred and mostof the toluene removed under reduced pressure. DMF (50 mL), DMAP (65mg), triethylamine (1.1 mL), hydroquinone (20 mg) and crotonic anhydride(1.23 g, 7.98 mmol) were added. After being stirred at room temperaturefor 24 hours the reaction mixture was drowned into water (200 mL) andthe mixture allowed to stand for awhile. The functionalized red dye wascollected by filtration, washed with water and dried in vacuo. The yieldwas 1.96 g of product (83% of the theoretical yield). FDMS supported thefollowing structure:

[0082] An absorption maximum at 529 nm was observed in the UV-visiblelight absorption spectrum.

Example 16

[0083] A mixture of 1,5-bis-(2,2-dimethyl-3-hydroxypropylamino)anthraquinone (U.S. Pat. No. 4,999,418, Example 1) (2.0 g, 4.88 mmol)and toluene (10 mL) was stirred and most of the toluene was removedunder reduced pressure. DMF (50 mL), DMAP (120 mg), triethyl amine (2.0mL) and crotonic anhydride (2.25 g, 14.6 mmol) were added. The reactionmixture was stirred at room temperature for 24 hours and then drownedinto water (200 mL) and the mixture allowed to stand awhile. Thefunctionalized red dye was collected by filtration, washed with waterand dried in vacuo. The yield was 2.24 g (98% of the theoretical yield).FDMS supported the following structure:

[0084] An absorption maximum at 527 nm was observed in the UV-visiblelight spectrum in DMF as the solvent.

Example 17

[0085] A mixture of a portion (2.0 g, 3.33 mmol) of the dye of Example7a above and toluene (10 mL) was stirred and most of the toluene removedunder vacuum. DMF (50 mL), DMAP (86 mg) triethylamine (1.4 mL),hydroquinone (20 mg) and crotonic anhydride (7.54 g, 9.99 mmol) wereadded. The reaction mixture was stirred at room temperature for 24 hoursand drowned into water (200 mL) with stirring. The mixture was allowedto stand awhile and the functionalized yellow dye was collected byfiltration, washed with water and dried in vacuo (yield 2.01 g, 82% ofthe theoretical yield). FDMS supported the following structure:

[0086] An absorption maximum at 446 nm was observed in DMF in theUV-visible light absorption spectrum.

Example 18

[0087] A mixture of 1,5-bis-(2,2-dimethyl-3-hydroxypropylamino)anthraquinone (U.S. Pat. No. 4,999,418, Example 1) (1.0 g, 2.44 mmol)and toluene (50 mL) was stirred and most of the toluene removed underreduced pressure. DMF (50 mL), DMAP (60 mg), triethylamine (1.0 mL),hydroquinone (50 mg) and cinnamoyl chloride (Aldrich; 1.22 g, 7.35 mmol)were added. The reaction mixture was stirred at about 50° C. temperaturefor about 12 hours and then drowned into water (100 mL). Thefunctionalized red dye was collected by filtration, washed with waterand dried in vacuo (yield—1.61 g, 99% of the theoretical yield). FDMSsupports the following structure:

[0088] An absorption maximum at 527 nm was observed in DMF in theUV-visible absorption spectrum.

[0089] The functionalized dyes or colorants which contain vinyl orsubstituted vinyl groups are polymerizable or copolymerizable,preferably by free radical mechanisms, said free radicals beinggenerated by exposure to UV light by methods known in the art ofpreparing UV-cured resins. Polymerization can be facilitated by theaddition of photoinitiators. The colored polymeric materials normallyare prepared by dissolving the functionalized colorants containingcopolymerizable groups in a polymerizable vinyl monomer with or withoutanother solvent and then combining with an oligomeric or polymericmaterial which contains one or more vinyl or substituted vinyl groups.

[0090] The second embodiment of the present invention is a coatingcomposition comprising (i) one or more polymerizable vinyl compounds,i.e., vinyl compounds which are copolymerizable with the dye compoundsdescribed herein, (ii) one or more of the dye compounds described above,and (iii) at least one photoinitiator. The polymerizable vinyl compoundsuseful in the present invention contain at least one unsaturated groupcapable of undergoing polymerization upon exposure to UV radiation inthe presence of a photoinitiator, i.e., the coating compositions areradiation-curable. Examples of such polymerizable vinyl compoundsinclude acrylic acid, methacrylic acid and their anhydrides; crotonicacid; itaconic acid and its anhydride; cyanoacrylic acid and its esters;esters of acrylic and methacrylic acids such as allyl, methyl, ethyl,n-propyl, isopropyl, butyl, tetrahydrofurfuryl, cyclohexyl, isobornyl,n-hexyl, n-octyl, isooctyl, 2-ethylhexyl, lauryl, stearyl, and benzylacrylate and methacrylate; and diacrylate and dimethacrylate esters ofethylene and propylene glycols, 1,3-butylene glycol, 1,4-butanediol,diethylene and dipropylene glycols, triethylene and tripropyleneglycols, 1,6-hexanediol, neopentyl glycol, polyethylene glycol, andpolypropylene glycol, ethoxylated bisphenol A, ethoxylated andpropoxylated neopentyl glycol; triacrylate and trimethacrylate esters oftris-(2-hydroxyethyl)isocyanurate, trimethylolpropane, ethoxylated andpropoxylated trimethylolpropane, pentaerythritol, glycerol, ethoxylatedand propoxylated glycerol; tetraacrylate and tetramethacrylate esters ofpentaerythritol and ethoxylated and propoxylated pentaerythritol;acrylonitrile; vinyl acetate; vinyl toluene; styrene; N-vinylpyrrolidinone; alpha-methylstyrene; maleate/fumarate esters;maleic/fumaric acid; crotonate esters, and crotonic acid.

[0091] The polymerizable vinyl compounds useful in the present inventioninclude polymers which contain unsaturated groups capable of undergoingpolymerization upon exposure to UV radiation in the presence of aphotoinitiator. The preparation and application of these polymerizablevinyl compounds are well known to those skilled in the art as described,for example, in Chemistry and Technology of UV and EB Formulation forCoatings, Inks, and Paints, Volume II: Prepolymers and ReactiveDiluents, G. Webster, editor, John Wiley and Sons, London, 1997.Examples of such polymeric, polymerizable vinyl compounds includeacrylated and methacrylated polyesters, acrylated and methacrylatedpolyethers, acrylated and methacrylated epoxy polymers, acrylated ormethacrylated urethanes, acrylated or methacrylated polyacrylates(polymethacrylates), and unsaturated polyesters. The acrylated ormethacrylated polymers and oligomers typically are combined withmonomers which contain one or more acrylate or methacrylate groups,e.g., monomeric acrylate and methacrylate esters, and serve as reactivediluents. The unsaturated polyesters, which are prepared by standardpolycondensation techniques known in the art, are most often combinedwith either styrene or other monomers, which contain one or moreacrylate or methacrylate groups and serve as reactive diluents. A secondembodiment for the utilization of unsaturated polyesters that is knownto the art involves the combination of the unsaturated polyester withmonomers that contain two or more vinyl ether groups or two or morevinyl ester groups (WO 96/01283, WO 97/48744, and EP 0 322 808).

[0092] The coating compositions of the present invention optionally maycontain one or more added organic solvents if desired to facilitateapplication and coating of the compositions onto the surface ofsubstrates. Typical examples of suitable solvents include, but are notlimited to ketones, alcohols, esters, chlorinated hydrocarbons, glycolethers, glycol esters, and mixtures thereof. Specific examples include,but are not limited to acetone, 2-butanone, 2-pentanone, ethyl acetate,propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate,ethylene glycol diacetate, ethyl 3-ethoxypropionate, methyl alcohol,ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol,ethylene glycol, propylene glycol, ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, ethylene glycol monopropyl ether,ethylene glycol monobutyl glycol, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,propylene glycol monomethyl ether, diethylene glycol monobutyl etheracetate, diethylene glycol monoethyl ether acetate, ethylene glycolmonobutyl ether acetate, propylene glycol monomethyl ether acetate,methylene chloride, chloroform, and mixtures thereof. The amount ofadded or extraneous solvent which may be present in our novel coatingcompositions may be in the range of about 1 to 70 weight percent, moretypically about 1 to 25 weight percent, based on the total weight of thecoating composition.

[0093] Certain polymerizable vinyl monomers may serve as both reactantand solvent. These contain at least one unsaturated group capable ofundergoing polymerization upon exposure to UV radiation in the presenceof a photoinitiator. Specific examples include, but are not limited to:methacrylic acid, acrylic acid, ethyl acrylate and methacrylate, methylacrylate and methacrylate, hydroxyethyl acrylate and methacrylate,diethylene glycol diacrylate, trimethylolpropane triacrylate, 1,6hexanediol di(meth)acrylate, neopentyl glycol diacrylate andmethacrylate, vinyl ethers, divinyl ethers such as diethyleneglycoldivinyl ether, 1,6-hexanediol divinyl ether, cyclohexanedimethanoldivinyl ether, 1,4-butanediol divinyl ether, triethyleneglycol divinylether, trimethylolpropane divinyl ether, and neopentyl glycol divinylether, vinyl esters, divinyl esters such as divinyl adipate, divinylsuccinate, divinyl glutarate, divinyl 1,4-cyclohexanedicarboxylate,divinyl 1,3-cyclohexanedicarboxylate, divinyl isophthalate, and divinylterephthalate, N-vinyl pyrrolidone, and mixtures thereof.

[0094] In addition, the compositions of the present invention may bedispersed in water rather than dissolved in a solvent to facilitateapplication and coating of the substrate surface. In the water-dispersedcompositions of the present invention a co-solvent is optionally used.Typical examples of suitable cosolvents include but are not limited toacetone, 2-butanone, methanol, ethanol, isopropyl alcohol, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethyleneglycol monopropyl ether, and ethylene glycol monobutyl ether, ethyleneglycol, and propylene glycol. Typical examples of water-solubleethylenically unsaturated solvents include but are not limited to:methacrylic acid, acrylic acid, N-vinyl pyrrolidone, 2-ethoxyethylacrylate and methacrylate, polyethylene glycol dimethacrylate,polypropylene glycol monoacrylate and monomethacrylate, and mixturesthereof. The amount of suitable aqueous organic solvent (i.e., organicsolvent and water) in the dispersed coating compositions of the presentinvention is about 10 to about 90 weight percent, preferably about 75 toabout 90 weight percent of the total coating composition.

[0095] The coating compositions of the present invention contain one ormore of the reactive vinyl dye compounds described herein. Theconcentration of the dye compound or compounds may be from about 0.005to 30.0, preferably from about 0.05 to 15.0, weight percent based on theweight of the polymerizable vinyl compound(s) present in the coatingcomposition, i.e., component (i) of the coating compositions. Thecoating compositions of the present invention normally contain aphotoinitiator. The amount of photoinitiator typically is about 1 to 15weight percent, preferably about 3 to about 5 weight percent, based onthe weight of the polymerizable vinyl compound(s) present in the coatingcomposition. Typical photoinitiators include benzoin and benzoin etherssuch as marketed under the tradenames ESACURE BO, EB1, EB3, and EB4 fromFratelli Lamberti; VICURE 10 and 30 from Stauffer; benzil ketals such as2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE 651),2-hydroxy-2-methyl-1-phenylpropan-1-one (IRGACURE 1173),2-methyl-2-morpholino-1-(p-methylthiophenyl)propan-1-one (IRGACURE 907),alpha-hydroxyalkylphenones such as(1-hydroxycyclohexyl)(phenyl)-methanone (IRGACURE 184),2-benzyl-2-(dimethylamino)-1-(4-morpholino-phenyl)butan-1-one (IRGACURE369), 2-hydroxy-2-methyl-1-phenylpropan-1-one IRGACURE 1173) from CibaGeigy, Uvatone 8302 by Upjohn; alpha, alpha-dialkoxyacetophenonederivatives such as DEAP and UVATONE 8301 from Upjohn; DAROCUR 116,1173, and 2959 by Merck; and mixtures of benzophenone and tertiaryamines In pigmented coating compositions, the rate of cure can beimproved by the addition of a variety of phosphine oxide photoinitiaterssuch as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irganox 819),Irgacure 819, 1700, and 1700 and phosphine oxide mixtures such as a50/50 by weight mixtures of IRGACURE 1173 and2,4,6-trimethylbenzoyldiphenyl-phosphine oxide (DAROCUR 4265) from Ciba.Further details regarding such photoinitiators and curing procedures maybe found in the published literature such as U.S. Pat. No. 5,109,097,incorporated herein by reference. Depending upon the thickness of thecoating (film), product formulation, photoinitiator type, radiationflux, and source of radiation, exposure times to ultraviolet radiationof about 0.5 second to about 30 minutes (50-5000 mJ/square cm) typicallyare required for curing. Curing also can occur from solar radiation,i.e., sunshine.

[0096] The coating compositions of the present invention may contain oneor more additional components typically present in coating compositions.Examples of such additional components include leveling, rheology, andflow control agents such as silicones, fluorocarbons or cellulosics;flatting agents; pigment wetting and dispersing agents; surfactants;ultraviolet (UV) absorbers; Uv light stabilizers; tinting pigments;defoaming and antifoaming agents; anti-settling, anti-sag and bodyingagents; anti-skinning agents; anti-flooding and anti-floating agents;fungicides and mildewcides; corrosion inhibitors; thickening agents;and/or coalescing agents. The coating compositions of the presentinvention also may contain non-reactive modifying resins. Typicalnon-reactive modifying resins include homopolymers and copolymers ofacrylic and methacrylic acid; homopolymers and copolymers of alkylesters of acrylic and methacrylic acid such as methyl, ethyl, n-propyl,isopropyl, butyl, tetrahydrofurfuryl, cyclohexyl, isobornyl, n-hexyl,n-octyl, isooctyl, 2-ethylhexyl, lauryl, stearyl, and benzyl acrylateand methacrylate; acrylated and methacrylated urethane, epoxy, andpolyester resins, silicone acrylates, cellulose esters such as celluloseacetate butyrates, cellulose acetate, propionates, nitrocellulose,cellulose ethers such as methyl cellulose, ethyl cellulose,hydroxypropyl cellulose, and hydroxypropyl methyl cellulose.

[0097] Typical plasticizers include alkyl esters of phthalic acid suchas dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutylphthalate, and dioctyl phthalate; citrate esters such as triethylcitrate and tributyl citrate; triacetin and tripropionin; and glycerolmonoesters such as Eastman 18-04, 18-07, 18-92 and 18-99 from EastmanChemical Company. Specific examples of additional additives can be foundin Raw Materials Index, published by the National Paint & CoatingsAssociation, 1500 Rhode Island Avenue, N.W., Washington, D.C. 20005.

[0098] The third embodiment of the present invention pertains to apolymeric composition, typically a polymeric coating, comprising apolymer of one or more acrylic acid esters, one or more methacrylic acidesters and/or other polymerizable vinyl compounds, having copolymerizedtherein one or more of the dye compounds described above. The coloredpolymeric compositions provided by our invention may be prepared fromthe coating compositions described above and typically contain fromabout 0.005 to 30.0 weight percent, preferably from about 05 to 15.0weight percent, of the reactive or polymerized residue of one or more ofthe vinyl dye compounds described herein based on the weight of thecomposition or coating. The novel polymeric coatings may have athickness of about 2.5 to 150 microns, more typically about 15 to 65microns.

[0099] The polymeric coatings of the present invention typically have asolvent resistance of at least 100 MEK double rubs using ASTM ProcedureD-3732; preferably a solvent resistance of at least about 200 doublerubs. Such coatings also typically have a pencil hardness of greaterthan or equal to F using ASTM Procedure D-3363; preferably a pencilhardness of greater than or equal to H. The coating compositions can beapplied to substrates with conventional coating equipment. The coatedsubstrates are then exposed to radiation such as ultraviolet light inair or in nitrogen which gives a cured finish. Mercury vapor or Xenonlamps are applicable for the curing process. The coatings of the presentinvention can also be cured by electron beam.

[0100] The radiation-curable coating compositions of this invention aresuitable as adhesives and coatings for such substrates as metals such asaluminum and steel, plastics, glass, wood, paper, and leather. On woodsubstrates the coating compositions may provide both overall transparentcolor and grain definition. Various aesthetically-appealing effects canbe achieved thereby. Due to reduced grain raising and higher filmthicknesses, the number of necessary sanding steps in producing afinished wood coating may be reduced when using the colored coatingcompositions of the invention rather than conventional stains. Coatingcompositions within the scope of our invention may be applied toautomotive base coats where they can provide variousaesthetically-appealing effects in combination with the base coats andcolor differences dependent on viewing angle (lower angles create longerpath lengths and thus higher observed color intensities). This mayprovide similar styling effects as currently are achieved with metalflake orientation in base coats.

[0101] Various additional pigments, plasticizers, and stabilizers may beincorporated to obtain certain desired characteristics in the finishedproducts. These are included in the scope of the invention.

[0102] Coatings Curing and Testing Procedures:

[0103] Samples of formulations were used to coat glass plates using aknife blade. The wet film thickness was about 15 to 75 microns (0.6 to3.0 mils). The solvent was evaporated to give a clear, somewhat tackyfilm. Prior to exposure to UV radiation, each film was readily solublein organic solvents.

[0104] The dried film on the glass plate was exposed to UV radiationfrom a 200 watt per inch medium pressure mercury vapor lamp housed in anAmerican Ultraviolet Company instrument using a belt speed of 25 ft. perminute. One to five passes under the lamp resulted in a crosslinkedcoating with maximum hardness and solvent resistance.

[0105] Each cured coating (film) may be evaluated for Konig PendulumHardness (ASTM D4366 DIN 1522), solvent resistance by the methyl ethylketone double-rub test, and solubility in acetone before and afterexposure to UV radiation. The damping time for Konig Pendulum Hardnesson uncoated glass is 250 seconds; coatings with hardness above 100seconds are generally considered hard coatings. The methyl ethyl ketone(MEK) double rub test is carried out in accordance with ASTM ProcedureD-3732 by saturating a piece of cheese cloth with methyl ethyl ketone,and with moderate pressure, rubbing the coating back and forth. Thenumber of double rubs is counted until the coating is removed. Theacetone solubility test is carried out by immersing a dry, pre-weighedsample of the cured film in acetone for 48 hours at 25° C. The film isremoved, dried for 16 hours at 60° C. in a forced-air oven, andreweighed. The weight percent of the insoluble film remaining iscalculated from the data.

[0106] Coating Examples

[0107] The coatings and coating compositions provided by the presentinvention and the preparation thereof are further illustrated by thefollowing examples.

Example 19

[0108] A colored, photopolymerizable composition was prepared bythoroughly mixing 22.9 g of dipropylene glycol diacrylate, 69.1 g ofJaegalux UV-1500 (acrylated polyester oligomers), the red dye of Example8 (4 g of a 1.25% solution of the dye in dipropylene glycol diacrylate),and 4 g of Darocure 1173 photoinitiator in a small Cowles mixer untilthe components were completely dispersed. This coating composition wasdrawn down with a wire wound rod to provide a 25.4 micron (1 mil) thickcoating on an Oak wood panel. This panel was passed through a UV curemachine at a speed of 6.1 meters per minute (20 feet/minute) using alamp with an intensity of 118.1 watts per cm (300 watts per inch). Thesame colored, photopolymerizable composition was applied to glass panelsand cured under the same conditions of exposure. The hardness of thecured coating on the glass panels was 83 Konig seconds as compared to ahardness of 82 Konig seconds for a reference coating which contained nopolymerizable dye. Adhesion of the coating to an oak wood panel wasmeasured using the crosshatch adhesion method according to ASTM method D3359 (ISO 2409). A right angle lattice pattern (6 lines in eachdirection) is cut into the coating, penetrating to the substrate,creating 25 squares with each side of the squares measuring 1 mm. A 2.5cm (1 inch) wide piece of tape is applied to the lattice, pressure isapplied, and then the tape is pulled from the substrate. If the edgesare smooth and none of the squares are detached, the adhesion is 100%(ASTM rating 5B). On the wood panel a 5B rating was achieved for boththe reference and the dye-containing coatings. On glass both coatingsfailed completely. Chemical resistance was tested with MEK double rubson glass. Both the reference, which contained no polymerizable dye, andthe coatings, which contained polymerizable dyes, withstood more than300 MEK double rubs. No dye color could be observed on the whitecheesecloth of the MEK rub test, which is an indication that the dyescannot be extracted from the coatings with solvents and suggestscomplete incorporation of the dye into the polymer matrix of the curedfilm.

Example 20

[0109] A colored, photopolymerizable composition was prepared bythoroughly mixing 22.9 g of dipropylene glycol diacrylate, 69.1 g ofJaegalux UV-500 (acrylated polyester oligomers), the blue dye having thestructure:

[0110] (4 g of a 1.25% solution of the dye in dipropylene glycoldiacrylate), and 4 g of Darocure 1173 photoinitiator in a small Cowlesmixer until the components were completely dispersed. This coatingcomposition was drawn down with a wire wound rod to provide a 25.4micron (1 mil) thick coating on an Oak wood panel.

[0111] This panel was passed through a UV cure machine at a speed of 6.1meters per minute (20 feet/minute) using a lamp with an intensity of118.1 watts per cm (300 watts per inch). Hardness measurements wereconducted on glass using a Konig pendulum and did not indicate anysignificant loss of hardness due to incorporation of the dye; hardnesswas 83 Konig seconds. Adhesion of the coating to an oak wood panel wasmeasured using the crosshatch adhesion method described in Example 19.On the wood panel a 5B rating was achieved for both the reference andthe dye-containing coatings. All the coatings withstood more than 300MEK double rubs. No loss of solvent resistance was observed withincorporation of the dye.

Example 21

[0112] A colored, photopolymerizable composition was prepared bythoroughly mixing 22.9 g of dipropylene glycol diacrylate, 69.1 g ofJaegalux UV-1500 (acrylated polyester oligomers), the red dye of Example8 (2 g of a 1.25% solution of the dye in dipropylene glycol diacrylate),the blue dye set forth in Example 20 (2 g of a 1.25% solution of the dyein dipropylene glycol diacrylate), and 4 gram of Darocure 1173photoinitiator in a small Cowles mixer until the components werecompletely dispersed. This coating composition, which is purple due tothe mixing of the red and blue dyes, was drawn down with a wire woundrod to provide a 25.4 micron (1 mil) thick coating on an Oak wood panel.This panel was passed through a UV cure machine at a speed of 6.1 metersper minute (20 feet/minute) using a lamp with an intensity of 118.1watts per cm (300 watts per inch). Hardness measurements were conductedon glass using a Konig pendulum and did not indicate any significantloss of hardness due to incorporation of the dye; hardness was 83 Konigseconds. Adhesion of the coating to an oak wood panel was measured usingthe crosshatch adhesion method described in Example 19. On the woodpanel a 5B rating was achieved for both the reference coating and thedye-containing coatings. All of the coatings withstood more than 300 MEKdouble rubs. No significant loss of solvent resistance was observed withincorporation of the dye.

Example 22

[0113] A colored, photopolymerizable composition was prepared bythoroughly mixing 10.0 g dipropylene glycol diacrylate, 10.0 gtripropylene gylcol triacrylate, 20.0 g Jaegalux UV-1500 (acrylatedpolyester oligomers), 15 g Jaegalux UV-3800 (acrylated epoxy oligomers),the blue dye set forth in Example 20 (5.5 g of a 1.25% solution of thedye in dipropylene glycol diacrylate), and 2.2 gram of Irgacure 819photoinitiator in a small Cowles mixer until the components werecompletely dispersed (20 minutes at 12,000 revolutions per minute). Thiscoating composition was drawn down with a wire wound rod to provide a38.1 micron (1.5 mil) thick coating on a cold rolled steel panel (ironphosphate pretreatment) and on polyethylene terephthalate sheet. Thecoated steel panel and polyester sheet were passed through a UV curemachine at a speed of 6.1 meters per minute (20 feet/minute) using alamp with an intensity of 118.1 watts per cm (300 watts per inch). TheKonig pendulum hardness of the coatings on the steel panels was 126Konig seconds. No significant loss of hardness (relative to thereference coating) due to incorporation of the dye was observed. All thecoatings withstood more than 500 MEK double rubs. No significant loss ofsolvent resistance was observed with incorporation of the dye. Adhesiontests of the coatings on polyethylene terephthalate sheeting using thecrosshatch adhesion method described in Example 19 showed no loss ofadhesion due to incorporation of the dye and 100% adhesion for thecoatings.

Example 23

[0114] A colored, photopolymerizable composition was prepared bythoroughly mixing the blue dye set forth in Example 20 (10 g of a 2%solution of the dye in dipropylene glycol diacrylate), 20 gramtrimethylol propane triacrylate, 20 g of polyester acrylate oligomer, 15g of bisphenol A epoxy acrylate, and 4 gram of PI 1173 photoinitiator ina small Cowles mixer until the components were completely dispersed. Theresulting coating composition was drawn down with a wire wound rod toprovide a 25.4 micron (1 mil) thick coating on a 20 gauge sheet (1.27mm-50 mils-thick) of polyethylene terephthalate (PET). The coated sheetwas passed through a LV cure machine at a speed of 6.1 meters per minute(20 feet/minute) using a lamp with an intensity of 118.1 watts per cm(300 watts per inch). Hardness measured on glass by the Konig Pendulummethod indicated no reduction of the hardness due to the dye; hardnesswas 105 Konig seconds. Adhesion tests of the coatings on polyethyleneterephthalate sheet in accordance with the crosshatch adhesion methoddescribed in Example 19 showed no loss of adhesion due to incorporationof the dye and 100% adhesion for the coatings. All the coatingswithstood more than 300 MEK double rubs. No significant loss of solventresistance was observed with incorporation of the dye. The coatingprovided an attractive even color over the entire coated sheet.

Example 24

[0115] A colored, photopolymerizable composition was prepared bythoroughly mixing 0.5 g the yellow dye of Example 9 with a coatingcomposition consisting of 20 g Jägalux UV 1500 polyester acrylate, 10 gof bisphenol A epoxy acrylate, 9 g dipropyleneglycol diacrylate (DPGDA),7 g trimethylolpropane triacrylate (TMPTA), and 4 g of Darocure 1173photoinitiator using a small Cowles mixer until the components werecompletely dispersed. The resulting coating composition containing 1% ofthe yellow dye was drawn down with a wire wound rod to provide a 25.4micron (1 mil) thick coating on an oak wood panel. This panel was passedthrough a UV cure machine at a speed of 6.1 meters per minute (20feet/minute) using a lamp with an intensity of 118.1 watts per cm (300watts per inch). The same coating solutions were applied to glass panelsand cured under the same conditions of exposure. Konig Pendulum Hardnessmeasurements (ASTM D4366 DIN 1522) were conducted on the coated glasspanels and indicated no significant loss of hardness due toincorporation of the dye; hardness was 86 Konig seconds compared with 82seconds for a reference coating, which contained no polymerizable dye.Adhesion of the coating to an oak wood panel was measured using thecrosshatch adhesion method described in Example 19. On the wood panel a5B rating was achieved for both the reference and the dye-containingcoatings. Chemical resistance was tested with MEK double rubs on glass.Both the reference, which contained no polymerizable dye, and thecoatings, which contained polymerizable dyes, withstood more than 300MEK double rubs. No dye color was observed on the white cheesecloth ofthe MEK rub test, which is an indication that the dyes cannot beextracted from the coatings with solvents and demonstrates completeincorporation of the dye into the polymer matrix of the cured film.

Example 25

[0116] A colored, photopolymerizable composition was prepared bythoroughly mixing 0.5 g the red dye of Example 10b with a coatingcomposition consisting of 20 g Jägalux UV1500 polyester acrylate, 10 gof bisphenol A epoxy acrylate, 9 g dipropyleneglycol diacrylate (DPGDA),7 g trimethylolpropane triacrylate (TMPTA), and 4 g of Darocure 1173photoinitiator in a small Cowles mixer until the components werecompletely dispersed. The resulting coating composition, which contained1% of the red dye, was drawn down with a wire wound rod to provide a25.4 micron (1 mil) thick coating on an oak wood panel. This panel waspassed through a UV cure machine at a speed of 6.1 meters per minute (20feet/minute) using a lamp with an intensity of 118.1 watts per cm (300watts per inch). The same coating solutions were applied to glass panelsand cured under the same conditions of exposure. Konig Pendulum Hardnessmeasurements conducted on the coated glass panels showed no significantloss of hardness due to incorporation of the dye; hardness was 76 Konigseconds compared with 82 seconds for a reference coating which containedno polymerizable dye.

[0117] The invention has been described in detail with particularreference to preferred embodiments thereof, but it will be understoodthat variations and modifications can be effected within the spirit andscope of the invention.

We claim:
 1. Anthraquinone dye compounds having the formulae:

wherein: R is selected from hydrogen or 1-3 groups selected fromC₁-C₆-alkyl, C₁-C₆-alkoxy and halogen; R₁ is selected from C₁-C₆-alkyl,substituted C₁-C₆-alkyl, C₃-C₈-alkenyl, C₃-C₈-cycloalkyl, aryl and-L₁-Z-Q; R₂=selected from hydrogen, C₁-C₆-alkyl, substitutedC₁-C₆-alkyl, C₃-C₈-cycloalkyl and aryl; R₃ and R₄ are independentlyselected from C₁-C₆-alkyl and bromine; R₅ is selected from C₁-C₆-alkyl,substituted C₁-C₆ alkyl, C₃-C₈-cycloalkyl, aryl, heteroaryl, -L₁-Z-Q,

R₆ is selected from

R₇ is selected from hydrogen, substituted or unsubstituted C₁-C₆-alkyl,C₁-C₆-alkoxy, halogen, hydroxy, substituted or unsubstitutedC₁-C₆-alkylthio, sulfamoyl and substituted sulfamoyl; R₈ is selectedfrom hydrogen and C₁-C₆-alkyl; R₉ is selected from the groupsrepresented by R₁ and -L-Z-Q; R₁₀ is selected from hydrogen and halogen;X is a covalent bond or a divalent linking group selected from —O—, —S—,—SO₂—, —CO₂—, —CON(Y)— and —SO₂N(Y)—, wherein Y is selected fromhydrogen, C₁-C₆-alkyl, substituted C₁-C₆-alkyl, C₃-C₈-cycloalkyl,C₃-C₈-alkenyl, aryl and -L-Z-Q; X₁ is selected from —O—, —S—, —SO₂— and—SO₂N(Y)—; X₂ is selected from —CO₂— and —SO₂N(Y₁), wherein Y₁ is agroup selected from hydrogen, C₁-C₆-alkyl, substituted C₁-C₆-alkyl,C₃-C₈-alkenyl, C₃-C₈₋cycloalkyl, aryl, heteroaryl and—CH₂-p-C₆H₄—C(R₈)═CH₂; X₃ is selected from —CO₂—, —SO₂N(Y)—; X₄ isselected from —CO₂—, —O— and —SO₂N(Y₁)—; L is a divalent linking groupselected from C₁-C₈-alkylene, C₁-C₆-alkylene-arylene, arylene,C₁-C₆-alkylene-arylene —C₁-C₆-alkylene, C₃-C₈-cycloalkylene,C₁-C₆-alkylene —C₃-C₈-cycloalkylene —C₁-C₆-alkylene,C₁-C₆-alkylene-Z₁-arylene -Z₁-C₁-C₆-alkylene andC₂-C₆-alkylene-[-Z₁-C₂-C₆-alkylene-]_(n)— wherein Z₁ is selected from—O—, —S— and —SO₂— and n is 1-3; L₁ is a divalent linking group selectedfrom C₂-C₆-alkylene, C₁-C₆-alkylene-C₃-C₈-cycloalkylene-C₁-C₆-alkylene,C₁-C₆-alkylene-arylene, C₃-C₈-cycloalkylene, andC₂-C₆-alkylene-[-Z₁-C₂-C₆-alkylene-]_(n)—; L₂ is selected fromC₂-C₆-alkylene, C₁-C₆-alkylene-arylene-C₁-C₆ alkylene andC₁-C₆-alkylene-C₃-C₈-cycloalkylene-C₁-C₆-alkylene; Z is a divalent groupselected from —O—, —S—, —NH—, —N(C₁-C₆-alkyl)-, —N(C₃-C₈ alkenyl)-,—N(C₃-C₈ cycloalkyl)-, —N(aryl)-, —N(SO₂C₁-C₆-alkyl) and —N(SO₂ aryl)-,provided that when Q is a photopolymerizable optionally substitutedmaleimide radical, Z represents a covalent bond; Q is anethylenically-unsaturated, photosensitive polymerizable group; and m andm₁ each is 0 or
 1. 2. Anthraquinone compounds according to claim 1wherein the ethylenically-unsaturated, photosensitive copolymerizablegroups represented by Q are selected from the following organicradicals:

wherein: R₁₁ is selected from hydrogen and C₁-C₆-alkyl; R₁₂ is selectedfrom hydrogen; C₁-C₆-alkyl; phenyl and phenyl substituted with one ormore groups selected from C₁-C₆-alkyl, C₁-C₆-alkoxy, —N(C₁-C₆-alkyl),nitro, cyano, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkanoyloxy and halogen; 1-and 2-naphthyl which may be substituted with C₁-C₆-alkyl orC₁-C₆-alkoxy; 2- and 3-thienyl which may be substituted with C₁-C₆-alkylor halogen; 2- or 3-furyl which may be substituted with C₁-C₆-alkyl; R₁₃and R₁₄ are selected from hydrogen, C₁-C₆-alkyl, substitutedC₁-C₆-alkyl, aryl or may be combined to represent a —[—CH₂—]₃₋₅—radical; R₁₅ is selected from hydrogen, C₁-C₆-alkyl, substitutedC₁-C₆-alkyl, C₃-C₈-alkenyl, C₃-C₈-cycloalkyl and aryl; R₁₆ is selectedfrom hydrogen, C₁-C₆-alkyl and aryl.
 3. Anthraquinone compoundsaccording to claim 2 having the formula:

wherein Z is —O—.
 4. Anthraquinone compounds according to claim 2 havingthe formula:

wherein Z is —O—.
 5. Anthraquinone compounds according to claim 2 havingthe formula:

wherein Z is —O—.
 6. Anthraquinone compounds according to claim 2 havingthe formula:

wherein Z is —O—.
 7. Anthraquinone compounds according to claim 2 havingthe formula:

wherein Z is —O—.
 8. Anthraquinone compounds according to claim 2 havingthe formula:

wherein Z is —O—.
 9. Anthraquinone compounds according to claim 2 havingthe formula:

wherein Z is —O—.
 10. Anthraquinone compounds according to claim 2having the formula:

wherein Z is —O—.
 11. Anthraquinone compounds according to claim 2having the formula:

wherein Z is —O—.
 12. Anthraquinone compounds according to claim 2having the formula:

wherein Z is —O—.
 13. Anthraquinone compounds according to claim 2having the formula:

wherein Z is —O—.
 14. Anthraquinone compounds according to claim 2having the formula:

wherein Z is —O—.
 15. Anthraquinone compounds according to claim 2having the formula:

wherein Z is —O—.
 16. Anthraquinone compounds according to claim 2having the formula:

wherein Z is —O—.
 17. Anthraquinone compounds according to claim 2having the formula:

wherein Z is —O—.
 18. Anthraquinone compounds according to claim 2having the formula:

wherein Z is —O—.
 19. Anthraquinone compounds according to claim 2wherein Q is organic radical Ia.
 20. Anthraquinone compounds accordingto claim 2 wherein Q is organic radical Ia wherein R₁₁ is hydrogen ormethyl and R₁₂ is hydrogen.
 21. Anthraquinone compounds according toclaim 2 wherein Q is organic radical VIIa.
 22. Anthraquinone compoundsaccording to claim 2 wherein Q is organic radical VIIa wherein R₁₁ ishydrogen.
 23. Anthraquinone compounds according to claim 2 wherein Q isorganic radical VIIIa.
 24. Anthraquinone compounds according to claim 2wherein Q is organic radical VIIIa wherein R₁₁ is hydrogen or methyl andR₁₃ and R₁₄ are methyl.
 25. Anthraquinone compounds according to claim 3wherein X is —CO₂—, L is —CH₂CH₂—, and m is
 1. 26. Anthraquinonecompounds according to claim 5 wherein L is —CH₂CH₂—, m is 1, and R₂ ishydrogen.
 27. Anthraquinone compounds according to claim 8 wherein L₁ is—CH₂C(CH₃)₂CH₂— and R₅ is aryl.
 28. Anthraquinone compounds according toclaim 9 wherein X is —CO₂—, L is —CH₂CH₂—, and m is
 1. 29. Anthraquinonecompounds according to claim 10 wherein L is —CH₂CH₂—, R₂ is hydrogenand m is
 1. 30. Anthraquinone compounds according to claim 12 wherein Xis —CO₂—, L is —CH₂CH₂—, and m is
 1. 31. Anthraquinone compoundsaccording to claim 13 wherein L is —CH₂CH₂—, R₂ is hydrogen and m is 1.32. Anthraquinone compounds according to claim 15 wherein X₃ is —CO₂—, Lis —CH₂CH₂—, and R is hydrogen or bromine.
 33. Anthraquinone compoundsaccording to claim 15 wherein X₃ is —CO₂—, L is propylene,1,4-cyclohexylenedimethylene or 2,2-dimethyltrimethylene, R is hydrogen,Z is —O—, and Q is an organic radical having the structure —COC(R₁₁)═CH₂wherein R₁₁ is hydrogen, methyl or ethyl.
 34. Anthraquinone compoundsaccording to claim 15 wherein X₃ is —CO₂—, L is propylene,1,4-cyclohexylenedimethylene or 2,2-dimethyltrimethylene, R is hydrogen,Z is —O—, and Q is an organic radical having structure VIIIa whereinR₁₁, R₁₃ and R₁₄ each is methyl.
 35. Anthraquinone compounds accordingto claim 16 wherein L₂ is —CH₂C(CH₃)₂CH₂—, and R₁₀ is hydrogen. 36.Anthraquinone compounds according to claim 17 wherein X₃ is —CO₂—, L is—CH₂CH₂—, and R is hydrogen.
 37. Anthraquinone compounds according toclaim 17 wherein X₃ is —CO₂—, L is propylene,1,4-cyclohexylenedimethylene or 2,2-dimethyltrimethylene, R is hydrogen,Z is —O—, and Q is an organic radical having the structure —COC(R₁₁)═CH₂wherein R₁₁ is hydrogen, methyl or ethyl.
 38. Anthraquinone compoundsaccording to claim 17 wherein X₃ is —CO₂—, L is propylene,1,4-cyclohexylenedimethylene or 2,2-dimethyltrimethylene, R is hydrogen,Z is —O—, and Q is an organic radical having structure VIIIa whereinR₁₁, R₁₃ and R₁₄ each is methyl.
 39. Anthraquinone compounds accordingto claim 18 wherein L is —CH₂CH₂—, R₂ is hydrogen, and m is
 1. 40.Anthraquinone compounds according to claim 6 wherein X is —SO₂N(Y)—, Lis C₂-C₆ alkylene, R₃ and R₄ are methyl or ethyl, Y is hydrogen, m is 1and m₁ is
 0. 41. Anthraquinone compounds according to claim 6 wherein Xis —SO₂N(Y)—, L is C₂-C₆ alkylene, R₃ and R₄ are methyl or ethyl, Y ishydrogen, m is 1 and m₁ is
 1. 42. Anthraquinone compounds according toclaim 1 having formula VII wherein X₂ is —CO2— and R and R₈ arehydrogen.
 43. Anthraquinone compounds according to claim 1 havingformula XI wherein X₂ is —CO2— and R₁ and R₈ are hydrogen. 44.Anthraquinone compounds according to claim 1 having formula XVII whereinX₄ is —CO2— and R and R₈ are hydrogen.
 45. Anthraquinone compoundsaccording to claim 1 having formula XXI wherein X₄ is —CO2— and R and R₈are hydrogen.
 46. Anthraquinone compounds according to claim 1 havingformula IV wherein X₁ is —O—, Z is —O—, L is —CH₂CH₂—, R₃ and R₄ aremethyl or ethyl, m is 1 and m₁ is
 0. 47. A coating compositioncomprising (i) one or more polymerizable vinyl compounds, (ii) one ormore of the dye compounds of claim 1, and (iii) a photoinitiator.
 48. Acoating composition according to claim 47 comprising (i) one or morepolymerizable vinyl compounds, (ii) one or more of the dye compounds ofclaim 2 present in a concentration of about 0.05 to 15 weight percentbased on the weight of component (i), and (iii) a photoinitiator presentin a concentration of about 1 to 15 weight percent based on the weightof the polymerizable vinyl compound(s) present in the coatingcomposition.
 49. A coating composition according to claim 48 wherein thepolymerizable vinyl compounds comprise a solution of a polymeric,polymerizable vinyl compound selected from acrylated and methacrylatedpolyesters, acrylated and methacrylated polyethers, acrylated andmethacrylated epoxy polymers, acrylated or methacrylated urethanes, andmixtures thereof, in a diluent selected from monomeric acrylate andmethacrylate esters.
 50. A polymeric coating composition comprising apolymer of one or more acrylic acid esters, one or more methacrylic acidesters and/or other copolymerizable vinyl compounds, havingcopolymerized therein one or more of the dye compounds defined inclaim
 1. 51. A polymeric composition according to claim 50 comprising acoating of an acrylic polymer of one or more acrylic acid esters, one ormore methacrylic acid esters or a mixture thereof having copolymerizedtherein one or more of the dye compounds defined in claim
 2. 52. Apolymeric composition according to claim 50 comprising a coating of anunsaturated polyester containing one or more maleate/fumarate residues;one or more monomers which contain one or more vinyl ether groups, oneor more vinyl ester groups, or a combination thereof, and, optionally,one or more acrylic or methacrylic acid esters; or a mixture thereofhaving copolymerized therein one or more of the dye compounds defined inclaim
 2. 53. A polymeric coating according to claim 51 containing fromabout 0.05 to 15.0 weight percent of the residue of one or more of thedye compounds of claim 2 based on the weight of the coating.